New sulphur-dyestuffs and alpha process of preparing them



Patented Nov. 8, i932 UNEE rear Fries 0N-THE-MAIN-FECI-IENHEIIJE, AND KARL LARBIG, 0F FRANKFOBT-ON-THE-MAIN-.

BIGGEST, GEBTIIANY, ASSIGNORS TO GENERAL ANILINE WORKS, IN (3., OF NEW YORK,

N. Y., A CORPORATEON OF DELAWARE NEW SULPHUR-DYESTUFFS AND A PROCESS OF PREPARING THEM No Drawing. Application filed November '3'; 1930, Serial No. 494,182, and in Germany November 19, 1929.

The present invention relates to new sulphur-dyestuiis and to a process of preparing 5 compounds as additions during the preparation of sulphur dyestuffs. According to Lange: Die Schrvefelfarbstotie 11, ed. 1925, there may be added, for instance, copper, zinc, manganese or iron compounds.

Now, we have found that sulphur-dyestuffs of a remarkable intensity of color and shade can be made by sulphurizing a parent material suitable for the preparation of sulphurdyestuffs in the presence of a compound of a metal of the group consisting of vanadium, uranium, tungsten, antimony and molybdenum. Starting materials for the preparations of sulphur dyestuffs are nitrophenols, aminophenols, indophenols, leuco-indophenols, azines and the like. In some cases it has proved advantageous to carry out the melting process in the presence of a mixture of one of the said metal compounds with another metal compound, especially a copper compound, or in the presence of a complex compound or" one or" the said metal compounds with another metal compound.

The dyestuffs obtainable according to this invention still contain the metal added during the sulphurization process; however, it is not known in which form the metal is present. They are of an extraordinary intensity of color and shade in comparison with the corresponding hitherto known dyestulls prepared without the said additions. Thus, for instance, when melting a suitable azine compound with a sulphurizing agent according to our process, red tints are obtainable which hitherto could not be produced in the group of sulphur-dyestuffs.

In locating the substituents in the phenazine compounds disclosed in some of the following examples and claims we employ the numbering of positions as shown in the following formula:

boa amt/K The following examples illustrate the invention, but they are not intended to limit it thereto, the parts being by weight:

1) 44 parts of alpha-naphthylamine and 35 parts of para-aminophenol are condensed in the usual manner with sodium hypochlorite solution so as to form indophenol. The latter is reduced by means of sodium sulphide, whereupon the leuc'o indophenol is precipitated by means of sodium bi-carbonate. The paste thus obtained is introduced into a solution of 150 parts of crystallized sodium sulphide and 100 parts of water of C. When the whole isdissolved, further 150 parts of sodium sulphide are added and the solution is heated to 80 C. Thereupon, a solution of 20 parts of ammonium molybdate in 50 parts of water is added and subsequently 110 parts of sulphur are introduced. The whole is heated to boiling and concentrated by evaporation until the boiling point of 122 C. to 124 C. is reached. At this temperature boiling is continued under reflux, until no more unchanged indophenol can be detected. The dyestuif is separated in the usual manner. There is obtained a productwhich dyes cotton from a sodium sulphide containing bath a vivid and intense bluish green tint. When no molybdate is added in the above process, a product is obtained yielding considerably more blue and more dull tints; by addition of copper salts a product is obtained yielding more yellow and more dull tints.

2) 42 parts of leuco indophenol, obtainable from 1-tolyl-aminonaphthalene-8-sulphonic acid and para-aminophenol, are boiled under reflux for hours with 58 parts of concentrated sodium sulphide, 47 parts of sulphur, 15 parts of ammonium molybdate and 125 parts of alcohol. 125 parts of water are then added, the alcohol is distilled 0E and, by addition of water, the solution is made up to 1250 parts. The dyestufi is then precipitated by passing a current of air through the solution at 50 C. It forms in the dry state a dark powder which dyes cotton very vivid bluish green tints.

3) 60 parts of crystallized sodium sulphide and 26 parts of sulphur are molten together and 7.5 parts of molybdic acid are added. Into this melt there are gradually introduced parts of 3-amino-Y-hydronyphenazine and the Whole is heated under reflux until the formation of the dyestuii is terminated. The crude melt may either be used directly for dyeing or the dyestuii may be isolated in the usual manner by precipitation by means of acid or air. The dyestufl dyes cotton beautiful reddish tints.

4) 7.5 parts of molybdenum sulphide are introduced, While stirring, into polysulphide prepared from 60 parts of crystallized sodium sulphide and'26 parts of sulphur. 15 parts oi 3-amino-7-hydroxyphenazine are then added and the Whole is ivorked up as described in Example A dyestuii' is obtained which is very similar to that obtainable accordingato Example 3. it yields, however, tints which are-not quite so red as those ob tainable by means of the dyestuff of EX- ample 3. i

parts of sulphur are dissolved in parts of crystallized sodium sulphide and.4l.5 parts or" the molybdic acid are added. Thereupon 15 parts of 2methyl-3-amino-6.8-d1- chloro Z-hydronyphenazine' are introduced and the Whole is Worked up as in Example The dyestuif obtained dyes cotton beautiful reddish tints.

6) 48 parts of sulphur are dissolved in 96 parts of crystallized sodium sulphide and after addition of a r-parts of molybdie acid 10 parts of 2-methyl-3-amino-Y- iydroxy-oethylphenazine are introduced. The Whole 7 is then heated until the formation of the dyestuff is finished. The dyestufi obtained dyes cotton reddish tints.

7) FJhen proceeding as in El a .ple 0, but adding besides the ingredients used in that Example l-part of copper sub iate, a dyestuiif is obtained which is very similar to that'obtainable according to Example 0.

v 8) 15 parts of 2-methyl-3amino-ThydroXy-5-ethylphenazine are introduced into a solution 01": 108 parts of crystallised sodium sulphide and 54 parts of sulphur at (1., a concentrated aqueous solution of 10 parts of sodium tungstate is added and the Whole is heated, after evapora ion of the ater, up to the boiling; point of 130 C. in the course of 30 hours and for about 10 hours at 130 C. Thereupon, the melt is diluted by addition o1 water to 500 parts and air is blown in at 80 C. until the dyestuii is precipitated completely. It forms in the dry state a violet powder and dyes cotton fun the bath a vivid bluish red tint. By substituting 1'? parts of uranyl nitrate for the sodium tungstate and proceeding in the same manner, a dyestufi" of a very similar tint is obtained.

. .Vhen'using 7 parts of ammonium molybdate instead of the above mentioned metal salts. a dyestufl is obtained yielding a con siderably more vivid and more yellowish tint. -vi hen replacing the sodium tungstate by 5 parts of ammonium vanadate, a dyestuff is obtained yielding less vivid and more violetish tints.

9) 1'? parts oi 2-methyl-3-amino-7-hydrosy-S-ethylphenazine used in Example 8 are introduced at about C in a 50% paste form into a solution a polysulphide prepared from 63 parts of crystallized sodium sulphide and 80 parts of sulphur at C. A concentrated aqueous solution of 3 parts of copper sulphate and 3 parts of ammonium molybdate is then added and the Whole is heated in the course of 5 hours up to the meltpoint 01 120 C. and then for 10 hours at C.1 l5 C. After cooling, the melt is pulverized and yields a dyestuff dyeing cotton from the sodium sulphide bath a vivid red tint.

10) Into a solution of parts of crystaL lized sodium sulphide 72 parts of sulphur and 20 parts of neutral sodium phosphate 20 parts or" 2-methyl-3-amino-7-hydroxy-5-ethylphenazine in paste form are introduced at about 100 C. and heated for 40 hours to 130 C. The mixture is worked up as indicated in Example 8. The dyestufl likewise dyes vivid red tints.

11) By using in Example 10 instead of the sodium phosphate 15 parts of potassium-antiinonyl-tartrate and proceeding in the manner indicated in that example, a dyestuft of a very similar tint is obtained.

12) 80 parts of crude cresol are boiled under reflux together with parts of crystallized sodium suphide, 7 5 parts of sulphur and 10 parts of ammonium molybdate at 120 C. for 2 hours. After-evaporation, the Whole is heated for 7 hours to 220 6.. for 2 hours to 2%0 (l. and for 2 hours to 250 C. and subsequently dissolved in 3000 parts of Water. The dyestuii" is then precipitated by means of hydrochloric acid. It dyes cotton from the sodium sulphide bath vivid brown tints.

Vi e claim:

1. In the process of preparing sulphurdyestuii's by melting an organic compound being; a starting material for the preparation of sulphur-dyestuffs With an alkali metal polysulphide the step which comprises carryinn" out the melting process in the presence of a compound of a metal of the group consisting' of molybdenum, tungsten, vanadium, uranium and antimony.

2. In the process of preparing sulphurdyestuiis by melting a phenazine compound with an alkali metal polysulphide the step which comprises carrying out the melting 7 process in the presence of a compound of a metal of the group consisting of molybdenum, tungsten, vanadium, uranium, and antimony.

3. In the process of preparing sulphur- 'dye'stufis by melting a phenazine of the fol wherein X stands for hydrogen or alkyl X stands for hydrogen or alkyl and X for hydrogen or amino, and v v Y and Y standfor hydrogen or halogen with an alkali metal polysulphide the step which comprises carrying out the melting process in the presence of an inorganic molybi denum compound.

4. In the process of preparing sulphurdyestufl'sby melting a phenazine of the following general formula i Y2 l 2 on,

3 0 r NH.

wherein X stands for hydrogen or ethyl Y and Y stand for hydrogen or chlorine with an alkali metal polysulphide the step which comprises carrying out the melting process in the presence of an inorganic molybdenum compound.

5. The process which comprises melting 2- methyl-3-amino-6.8- dichloro 7 oXy-phenazine with sodium polysulphide in the presence of molybdic acid.

6. The process which comprises melting 2- methyl-3-amino-7-oXy-5-ethylphenazine with sodium polysulphide in the presence of molybdic acid and copper sulphate.

7. The process which comprises melting 2-methyl 3-amino -7 oxy- 5-ethylphenazine with sodium polysulphide in the presence of ammonium molybdate and copper sulphate.

8. As new products, the sulphur-dyestuffs which are obtainable by melting an organic compound being a starting material for the preparation of sulphur dyestuifs with an alkali metal polysulphide in the presence of a compound of a metal of the group consisting of molybdenum, tungsten, Vanadium, uranium and antimony.

9. As new products, the sulphur-dyestuffs which are obtainable by melting a phenazine compound with an alkali metal polysulphide in the presence of a compound of a metal of the group consisting of molybdenum, tungsten, vanadium, uranium and antimony.

10. As new products, the sulphur-dyestuffs which are obtainable by melting a phenazine of the following general formula:

Q O 0 I r r X3 with "an alkali metal polysulphide stuffs which are obtainable by phenazineof the following general formula:

obtained from a wherein X stands for hydrogen or alkyl X for hydrogen or alkyl X for hydrogen or amino Y and Y stand for hydrogen or halogen in the presence ofan inorganic molybdenum compound; I a y 11. As new" products, the sulphur-dyem'elting a 1 Y N on; I

0 N \NHZ wherein X stands for hydrogen or ethyl g Y1 and Y stand for hydrogen or chlorine with an alkali metal polysulphide "in the presence of an inorganic molybdenum compound; V I

12. As a new-product, the sulphur-dyestuil which is obtainable by melting 2-methyl -3- amino-6.8-dichloro-Toxy-phenazine with sodium polysulphide in the presence of a molybdic acid. I I

13. As a new product, the sulphur-dyestuif which is obtainable by melting 2-methyl-3- am1no-7-oxy-5-ethyl-phenazine with sodium polysulphide in the presence of ammonium molybdate. Y 1 K i 14:. As new products, sulphur-dyestuffs obtained from an'organic compound being a starting material for the preparation of sulphur dyestuffs and a polysulphideand containing a metal of the group consistingof. molybdenum, tungsten, vanadium,; uranium'and antimony.

15. As new products, sulphur dyestulfs obtained from a phenazine and an alkali metal polysulphide and containing a metal of the group consisting of molybdenum,

tungsten, vanadium, uranium and antimony. 16. As 'new' products, sulphur-dyestuffs obtained from a phenazine of the following general formula 1 r X for hydrogen or alky-l 7 X forhydrogen or amino r I Y and Y stand for hydrogen or halogen and an alkali meta-lpolysulphide and containing'molybdenum.

17. 'As new products, sulphur-dyestuffs phenazine of the following general formula Y i wh r in X1 stands for hrdreee 9 thyl 1 and 2 an f l n reeen .0 chlor and an alkali metal re ysyl liids and e m l bde umlowing general formula;

Wh e-in X1 steed fe hyd og n r thy Y and Y stand for hydrogen or chlorin w th an alkali m t l ee s phi h s p which co rnp-rises carrying out the melting was #5 th Pr en .o n gan eelybdeeea em uncl and an inorganic were? QQ E P HQ A 2 A P9Flfla the ulphury stuffs whichare obtainable by melting an erganic co n-pound being a starting material 1ev undye ufis. an a relys ln d and-swetaining molybdenum angleopper,

26. As new products, su l bur-dyestuffs obtained from a phenaz inej of the following general formula:

fli ii Y1 X1 wherein X stands for hydrogen or ethyl,

Y and Y stand for hydrogen of chlorine, a d n alk l p ysul and c n a ing molybdenum and copper.

27. As a new product, a sulphur-dyestuff b ne r m .2-m hy -3-a n W -ph in nd dium p y ulphid and containing molybdenum and copper. v

In testimony whereof, we afiix'our signatures.

OTTO BAYER. WILHELM HOHENEMSER. KARL LARBIG.

foit the preparation of sulphur-dyestufis with an" al a m tal p' l s phide n th p es e ml l fil eu c mma a d a c pp m eeedn 23 As new products, the sulphursdyex rhish ar ebtaina le by m lt enazine of the following general formula:

rein X1 stands for hydrogen or ethyl,

Y and Y stand for hydrogen or chlorine,

v with an alkali metal .polySulphide in the presence of an inorganic molybdenum compeu d and, an ino ga i pper compound.

24. As a new product, the sulphur-dyestufi' which is obtainable by melting Q-methyl- '3 aming?-oxy 5;ethylphenazine with sodium polysulphide in the presence of ammonium molybdate and copper sulphate.

25. As new products, sulphur-dyestuffs obtained from an organic compound being a starting material for the preparation of sul- 

